Apparatus for catalytically reducing dioxygen using dirhodium complexes

ABSTRACT

Dirhodium complexes such as tetrakis (μ-2-anilinopyridinato)dirhodium are used in the catalytic reduction of dioxygen. An electric potential is applied to the dirhodium complex either dissolved in solution or supported by an electrode.

This is a division of pending application Ser. No. 258,849 filed Oct. 17, 1988, now U.S. Pat. No. 4,909,911.

BACKGROUND OF THE INVENTION

The present invention relates to processes and compositions for reducing dioxygen. More particularly, the present invention relates to a catalytic process using dirhodium complexes to reduce dioxygen.

Extensive efforts have gone into finding efficient catalysts that can promote the reaction of dioxygen with oxidizable substrates. Biological catalysts are effective in activation and transport of dioxygen. Accordingly, substantial work has been done with metalloporphyrin catalysts. However, there are few additional examples of transition-metal complexes that have the desired properties and reactivity to be utilized in the catalytic activation of dioxygen.

Activation of molecular oxygen by transition-metal complexes can occur by way of a one-electron-transfer process, a two-electron-transfer process, or a four-electron-transfer process which generate the superoxide ion, peroxide ion, or oxide ion in aprotic media. The superoxide ion, O₂ ⁻, is reactive towards some organic substrates either by nucleophilic substitution or by direct oxidation. Superoxide ions have been used for the degradation of chloroalkanes, chloroalkenes, and polychloro aromatic hydrocarbons. Solutions containing O₂ ⁻ can be prepared in aprotic solvents by electrochemical methods or by solublizing KO₂ with 18-crown-6-ether. However, there is still a need to find convenient and inexpensive pathways to generate O₂ ⁻.

A catalytic cycle involving manganese porphyrins for the reduction of dioxygen has been reported by S. E. Creager and R. W. Murray, "Electrochemical Reactivity of Manganese (II) Porphyrins. Effect of Dioxygen, Benzoic Anhydride, and Axial Ligands," 26 Inorg. Chem. 2612, (1987). Mixtures of the porphyrin and benzoic anhydride lead to a reduction of dioxygen at a control potential of -0.40V vs SCE. This process involved reduction by more than two electrons and heterolysis of the O--O bond by benzoic anhydride. However, the manganese porphyrin complex did not show catalytic behavior in the absence of benzoic anhydride.

Accordingly, it would be a significant advancement in the art to provide a catalyst and process for the continuous generation of superoxide ion. Such a catalyst and process are disclosed and claimed herein.

BRIEF SUMMARY OF THE INVENTION

The present invention is directed to an apparatus and process for the catalytic reduction of dioxygen utilizing dirhodium complexes. In a preferred embodiment, tetrakis (μ-2-anilinopyridinato)dirhodium is utilized to reduce dioxygen to form superoxide complexes. The superoxide ion can then be used in the formation of hydrogen peroxide or for the degradation of various organic substrates such as chloroalkanes, chloroalkenes, and polychloro aromatic hydrocarbons.

The preferred embodiment utilizes the isomer in which the four pyridine nitrogens of the anilinopyridine ligands are bound to one rhodium ion, and the four anilino nitrogens of the bridging ligands are bound to the second rhodium ion. The complex can be reduced in CH₂ Cl₂ in the presence of molecular oxygen; this will result in the formation of (ap)₄ Rh^(II) Rh^(III) (O₂ ⁻) where (ap)=2-anilinopyridinate ion. Further reduction at -0.48 V gives the superoxide complex, [(ap)₄ Rh^(II) ₂ (O₂ ⁻)]⁻.

In a second preferred embodiment, each rhodium is equatorially bound by two pyridine nitrogens and two anilino nitrogens trans to their own kind.

In additional preferred embodiments, dirhodium is bound to four 2-amino-4-methylpyridinate, 2-aminopyridinate, 5-chloro-2-aminopyridinate or 3,5-dichloro-2-aminopyridinate ligands through two amino and two pyridyl nitrogen donors in a cis arrangement.

The dirhodium complexes of the present invention can be applied to an electrode such as a carbon paste electrode so that the reduction of dioxygen can take place in an aqueous solution. The application of -0.48 V in the presence of molecular oxygen and water results in the formation of hydrogen peroxide.

BRIEF DESCRIPTION OF THE DRAWINGS

FIG. 1 is a schematic illustration of the structure of the preferred embodiment of a dirhodium complex of the present invention.

FIG. 2 is a schematic illustration of the structure of a second embodiment of a dirhodium complex of the present invention.

FIG. 3 is a schematic illustration of the structure of a third embodiment of a dirhodium complex of the present invention.

FIG. 4 is a scheme of the reaction mechanism of (ap)₄ Rh₂ (O₂ ⁻) under O₂ in CH₂ Cl₂.

DETAILED DESCRIPTION OF THE PREFERRED EMBODIMENTS

Tetrakis(μ-2-anilinopyridinato)dirhodium(II,III) cation, [(ap)₄ Rh^(II) Rh^(III) ]⁺, has four possible geometric isomers. Two of those isomers were synthesized and identified previously. J. L. Bear, L. M. Liu, and K. M. Kadish, "Structural, ESR, and Electrochemical Properties of Two [Rh₂ (ap)₄ ]⁺ Geometric Isomers (ap=2-Anilinopyridinate). A True Mixed-Valent Rhodium(II)-Rhodium(IIII) Complex," 26 Inorganic Chem. 2927-9 (1987). The teachings of the article are herein incorporated by reference.

The molecular structure of (ap)₄ Rh^(II) Rh^(III) Cl is shown in FIG. 1. This complex is the most polar of the four possible geometric isomers that could be formed by the 2-anilinopyridinate bridging ligand. Each of the rhodium ions is in a different equatorial ligand environment, and in addition, only one axial ligand bond is formed. This is true for either of the two formal oxidation states, (ap)₄ Rh₂ ^(II) or [(ap)₄ Rh^(II) Rh^(III) ]⁺. The chloride ion is bound to the rhodium with four pyridine nitrogen bonds, and this rhodium is probably the preferred binding site of dioxygen in the complexes to be discussed. The ESR spectrum of (ap)₄ Rh^(II) Rh^(III) Cl is unique among all other dirhodium complexes in that the odd electron is localized on one rhodium ion, showing the complex to contain a true Rh(II)-Rh(III) dimer unit.

The (ap)₄ Rh₂ Cl was synthesized by heating 300 mg of Rh₂ (OAc)₄ in 5 g of 2-anilinopyridine under vacuum at 130 °C for 24 h. Unreacted 2-anilinopyridine was removed by sublimation, and the solid mixture was then dissolved in a CH₂ Cl₂ solution containing CCl₄. Repeated purification on a silica gel column with 5% CH₃ OH in CH₂ Cl₂ gave a pure product in 40% yield.

The (ap)₄ Rh₂ ClO₄ was generated by reducing 50 mg of (ap)₄ Rh₂ Cl in CH₂ Cl₂, 0.05 M TBAP at -0.65 V vs. SCE under a CO atmosphere. The pinkish brown (ap)₄ Rh₂ (CO) product precipitates from solution. This precipitate was filtered and washed with cold CH₂ Cl₂. Carbon monoxide was removed, and (ap)₄ Rh₂ ClO₄ was generated by oxidizing the CO adduct at +0.2 V in CH₂ Cl₂, 0.1 M TBAP under an argon atmosphere. All electric potentials were measured versus a saturated calomel electrode.

All reagents for synthesis were used as received. Spectroscopic grade CH₂ Cl₂ was purified by distillation from CaH₂ under N₂. Dimethylformamide (DMF) was vacuum-distilled from 4-A activated molecular sieves, and tetrahydrofuran (THF) was distilled from CaH₂ followed by distillation over Na/benzophenone under N₂. The supporting electrolyte, tetra-n-butylammonium perchlorate (TBAP), was twice recrystallized from ethanol and dried in a vacuum oven at 40° C. Ultrahigh-purity O₂ (Big Three, Inc.) with a maximum of 3 ppm of H₂ O was used.

The (ap)₄ Rh₂ Cl undergoes a single reversible reduction at E_(1/2) =-0.38 V and a single reversible oxidation at E_(1/2) =+0.52 V in CH₂ Cl₂, 0.1 M TBAP. The bound Cl⁻ ion on (ap)₄ Rh₂ Cl can be replaced by ClO₄ ⁻ to give (ap)₄ Rh₂ ClO₄ and this leads to a 70-mV shift in the reduction potential and a 10-mV shift in the oxidation potential. (ap)₄ Rh₂ ^(II) is formed upon reduction at E_(1/2) =-0.31 V (process 1), while [(ap)₄ Rh₂ ^(III) ]²⁺ is generated upon oxidation at E_(1/2) =0.53 V (process 2).

The potentials for processes 1 and 2 do not change when oxygen is bubbled through the solution, but under these conditions, a new quasi-reversible reduction (process 3) appears at E₁₇₈ =0.48 V. The ratio of cathodic peak currents for process 3 to those for process 2 decreases with either an increase in scan rate or a decrease in temperature. This clearly indicates a reaction of electrogenerated (ap)₄ Rh₂ ^(II) with dioxygen.

The electrochemistry of (ap)₄ Rh₂ ClO₄ at a rotating Pt-disk electrode in the presence of O₂ gives results similar to those obtained by cyclic voltammetry. In the absence of dioxygen, the complex undergoes a one-electron reduction and a one-electron oxidation. However, in the presence of dioxygen, there are two one-electron reductions; the latter of which occurs at E₁₇₈ =0.48 V. There is no interference from the direct reduction of O₂, which occurs at E_(p) =-1.0 V in CH₂ Cl₂, 0.1 M TBAP at a scan rate of 0.10 V/s.

The ratio of the limiting current for process 3 to that for process 2 by rotating-disk voltammetry is 0.72 at 500 rpm, and the data thus suggest the following sequence of reactions:

    [(ap).sub.4 Rh.sup.II Rh.sup.III ].sup.+ +e.sup.- ⃡(ap).sub.4 Rh.sub.2.sup.II                                           (1)

    (ap).sub.4 Rh.sub.2.sup.II +O.sub.2 ⃡(ap).sub.4 Rh.sup.II Rh.sup.III (O.sub.2.sup.-)                                (2)

    (ap).sub.4 Rh.sup.II Rh.sup.III (O.sub.2.sup.-)+e.sup.- ⃡[(ap).sub.4 Rh.sub.2.sup.II (O.sub.2.sup.-)]-(3)

The ultimate product of the first reduction (2) is a dirhodium dioxygen adduct and is assigned as the rhodiumsuperoxide complex, (ap)₄ Rh^(II) Rh^(III) (O₂ ⁻), on the basis of its UV-visible spectrum, which clearly indicates the presence of a Rh^(II) Rh^(III) center.

Controlled-potential electrolysis of (ap)₄ Rh^(II) Rh^(III) (O₂ ⁻)was carried out in CH₂ Cl₂ under N₂ at -0.60 V, and the integrated current-time curve gave a total of 1.0±0.1 electrons transferred as the current decreased to zero. However, the residual current was larger when electrolysis of the same solution was carried out under an O₂ atmosphere. Under these conditions, the steady-state current did not decay to zero after 5 h of electrolysis, thus indicating that no significant decomposition of the complex occurred. The final steady-state current also did not vary with changes in the partial pressure of oxygen between 160 and 760 mmHg, suggesting that the reaction between (ap)₄ Rh₂ ^(II) and O₂ is pseudo first order with respect to the dirhodium complex. Finally, a turnover number of 4 was calculated when the bulk electrolysis of (ap)₄ Rh^(II) Rh^(III) (O₂ ⁻) was stopped after 1 h.

The above electrochemical results support a catalytic reduction of dioxygen in the sense that the original irreversible reduction of O₂ is shifted from E_(p) =-1.0 V in CH₂ Cl₂ containing 0.1 M TBAP to E₁₇₈ =-0.48 V in the same solution containing [(ap)₄ Rh^(II) Rh^(III) ]⁺. The reduction of (ap)₄ Rh^(II) Rh^(III) (O₂ ⁻) occurs at the Rh^(II) Rh^(III) center and results in the overall EC catalytic process shown in FIG. 4.

Route a in FIG. 4 involves an association-dissociation mechanism. [(ap)₄ Rh₂ ^(II) (O₂ ⁻)]⁻ undergoes dissociation of O₂ ⁻ to regenerate (ap)₄ Rh^(II) Rh^(III) (O₂ ⁻). The superoxide ion is known to react with CH₂ Cl₂ and gives as final products CH₂ O, Cl⁻, and O₂, and this reaction most likely occurs since no free O₂ ⁻ was detected by ESR in CH₂ Cl₂. The second process in FIG. 4 (route b) involved the direct attack of [(ap)₄ Rh₂ ^(II) (O₂ ⁻)]⁻ by a CH₂ Cl₂ solvent molecule, and this will also regenerate (ap)₄ Rh^(II) Rh^(III) (O₂ ⁻) under an O₂ atmosphere. Both processes a and b provide the necessary thermodynamic driving force to shift the reduction potential of O₂ through the electrode reduction of dirhodium oxygen adducts. The data obtained can be used to explain either process a or process b, and neither of the two possible routes can be eliminated. However, if route b occurs, the rate of the reaction of [(ap)₄ Rh₂ ^(II) (O₂ ⁻)]⁻ with CH₂ Cl₂ must be slow, since an ESR spectrum of this species is easily obtained in this solvent.

In a second preferred embodiment, each rhodium in the dirhodium complex is equatorially bound by two pyridine nitrogens and two anilino nitrogens trans to their own kind. Such a compound is illustrated in FIG. 2 which depicts a dirhodium(II) ion bridged by four 2-anilinopyridinate ions and one axial benzonitrile ligand.

FIG. 3 illustrates still another embodiment of the present invention comprising Bis(μ-2-para-methylamino-pyridine)bis(μ-2-para-methylaminopyridinato)dirhodium(II) trifluoroacetate.

Other dirhodium complexes also form part of the present invention. The complexes can be represented by the formula Rh₂ (L)₄ where L is a bridging ligand containing two donor atoms selected from the group consisting of N, S, P and O and combinations thereof provided that no more than one of the donor atoms in each ligand is O. Suitable ligands include amides, thioamides, amidines, and 2-aminopyridines. Substituted derivatives of these compounds can also be used.

Each rhodium atom in the dirhodium complexes of this invention is in a formal +1, +2 or +3 oxidation state. The final step in the activation (reduction) of dioxygen occurs at the rhodium centers through electron transfer from rhodium to O₂. The redox potential for this electron transfer process is controlled by the electron pair donor-acceptor ability of the four bridging ligands. preferably, the redox potential is within the range of +0.3 V to -0.5 V. Accordingly, other bridging ligands with similar donor-acceptor abilities of the bridging ligands of the preferred embodiments can be used in dirhodium complexes to achieve the desired catalytic properties.

The dirhodium catalysts can also be used to activate dioxygen in aqueous solutions. However, it is necessary to disburse the water insoluble dirhodium catalysts in a working electrode material. A suitable electrode can be made from carbon paste. The most common preparation of paste electrodes is by hand mixing graphite powder and Nujol in a 5 g/3 mL ratio in a mortar and pestle followed by blending in the desired weight of catalyst. A suitable electrode can be formed by hand coating the well mixed paste directly on a graphite plate of the desired surface area.

In a preferred embodiment, dirhodium complexes are prepared as discussed above. The preferred complex consists of a dirhodium unit bridged by four 2-anilinopyridinate ions and one axially bound chloride ion, Rh₂ (ap)₄ Cl. The ligands are arranged such that the four anilino nitrogens are bound to one rhodium ion and the second rhodium ion contains four equatorial pyridyl nitrogen bonds and one axial chloride bond as shown in FIG. 1.

The carbon paste is prepared by thoroughly mixing 5 g of graphite powder (UPS grade, Ultra Carbon, Inc.) and 3 mL Nujol oil (Aldrich). The dirhodium complex can then be doped into the graphite in a weight/weight ratio of about 2.5°.

Dirhodium(II,II) complex with 2-anilinopyridinate bridging ligand has been shown to reduce molecular oxygen to form a dirhodium(II,III) superoxide complex in aprotic solvents as discussed above. This complex undergoes a one electron reduction at -0.48 V to form a dirhodium(II,II) superoxide complex, [Rh₂ (ap)₄ (O₂)]⁻, which reacts with CH₂ Cl₂ or other superoxide scavengers to reform the original dirhodium(II,II) compound. Therefore, in the presence of dioxygen and at an applied potential of -0.48 V a catalytic cycle for the reduction of dioxygen is established. In aqueous solution the reaction of [Rh₂ (ap)₄ (O₂)]⁻ with H⁺ should facilitate superoxide dissociation in the form of HO₂ which disproportionates to form H₂ O₂ and O₂. The complex has an irreversible reduction wave at -0.4 V in this solvent. When one atm O₂ is bubbled through the solution, the intensity of the peak current is increased by nine times. The direct reduction of O₂ on a pure carbon paste electrode is not seen under the same condition, clearly indicating the electrocatalytical reduction of dioxygen by the dirhodium complex. The net charge flow is presumably due to the final formation of hydrogen peroxide after a reduction of O₂.

As can be seen from the foregoing, the present invention provides a unique process and apparatus for catalytically reducing dioxygen using a dirhodium catalyst. While the invention has been described with respect to the presently preferred embodiments, it will be appreciated by those skilled in the art that changes can be made to the invention without departing from its spirit or essential characteristics. For example, the dirhodium complexes of the present invention can be incorporated into other types of electrodes. Accordingly, all modifications or changes which come within the meaning and range of equivalency of the claims are to be embraced within their scope. 

What is claimed is:
 1. An apparatus for reducing oxygen in solution comprising an electrode containing a dirhodium complex of the formula Rh₂ (L)₄ wherein L is a ligand containing 2 donor atoms selected from the group consisting of N, S, P and O provided that not more than one of the donor atoms in each ligand is O and means for applying an electric potential.
 2. An apparatus for reducing dioxygen in solution comprising an electrode containing tetrakis(μ-2-anilinopyridinato)dirhodium and means for applying an electric potential. 